Tandem C−N Coupling for Acetamide Synthesis via Paired Electrolysis Using a Bifunctional Catalyst

Paired electrosynthesis of amide represents a route to conduct redox reactions under mild conditions. However, the individual design of anodic and cathodic catalysts can inherently cause interfacial and electronic mismatch of the electrodes, hindering the kinetic reactions across both electrodes and thus low efficiency. Herein, we present a cross-coupled paired electrolysis strategy integrating cathodic nitrite reduction (NO 2 RR) with anodic ethanol oxidation (EOR) to produce acetamide under ambient conditions, where a bifunctional NiCo 2 O 4 /NiCo-NCNT electrocatalyst establishes a unified catalytic framework that facilitates both half-reactions. The synergistic electrode reactions markedly enhance amide synthesis, achieving a yield of 815.47 μmol cm −2 h − 1 in a flow cell and enabling gram-scale production at current densities up to 310 mA cm −2 . In situ spectroscopic analysis confirms a cross-coupled tandem reaction mechanism over the bifunctional NiCo 2 O 4 /NiCo-NCNT electrocatalyst, driven by a synergistic interaction between the NiCo 2 O 4 phase and the NiCo-N x sites. Specifically, NiCo 2 O 4 at the anode oxidizes ethanol to generate CH 3 CHO, while NiCo-N x at the cathode promotes nitrite reduction to produce NH 3 via *NH 2 OH intermediates. The generated CH 3 CHO and NH 3 /NH 2 OH subsequently undergo interfacial coupling and C−N bond formation to yield acetamide. This study demonstrates an energy-efficient electrosynthesis of the valuable chemical acetamide.